CN103492861A - Manufacturing method for optical-electric-field enhancement device - Google Patents

Manufacturing method for optical-electric-field enhancement device Download PDF

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CN103492861A
CN103492861A CN201280016792.0A CN201280016792A CN103492861A CN 103492861 A CN103492861 A CN 103492861A CN 201280016792 A CN201280016792 A CN 201280016792A CN 103492861 A CN103492861 A CN 103492861A
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metal
electric field
optical electric
micro concavo
forms
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CN103492861B (en
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山添昇吾
纳谷昌之
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Fujifilm Corp
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    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
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Abstract

To manufacture an optical-electric-field enhancement device capable of detecting Raman-scattered light with high sensitivity in an easy and low cost manner. Form, on a substrate (11), a thin film (20) formed from a first metal or metal oxide, and form a micro-relief structure layer (22) formed from a hydroxide of the first metal or metal oxide by hydrothermally reacting the thin film (20) formed on the substrate (11), and then form a metallic micro-relief structure layer (24), formed from a second metal, on the surface of the micro-relief structure layer (22).

Description

The manufacture method of optical electric field enhance device
Technical field
The present invention relates to a kind of method that manufacture is equipped with the optical electric field enhance device of the micro concavo-convex metal construction that can induce local plasmon body excimer.
Background technology
It is known utilizing the senser element of the electric field enhancement effect due to local plasmon body excimer on metal surface and the electric field enhance device of Raman spectrum device.Raman spectroscopy is a technology that obtains the spectrum (Raman spectrum) of Raman diffused light by the spectral analysis scattered light, and is used to identify material, and wherein said scattering spectrum obtains by using single wavelength light beam to irradiate material.
A Raman spectroscopy that is called SERS (Surface enhanced raman spectroscopy) is arranged, and the optical electric field that this technology utilization strengthens by the resonance of local plasmon body excimer is amplified weak Raman diffused light (with reference to non-patent literature 1).What SERS utilized is following principle: while having on the metallic object of nanoscale jog on metallic object, particularly its surface when irradiation, at metallic object with when material contacts, because optical electric field occurs the resonance of local plasmon body excimer, strengthen, and the Raman scattering light intensity of the sample contacted with metal body surface is exaggerated.The Raman scattering that surface strengthens can be carried out as the carrier (substrate) that keeps tested object by adopting the substrate that has in its surface the metal concaveconvex structure.
The Si substrate that its surface is provided with jog is formed with metal film having on the described surface of jog, and it mainly is used as having in its surface the substrate (referring to Patent Document 1～3) of metal superfine concaveconvex structure.
In addition, also proposed the Al substrate, its surface is become metal oxide layer (Al by anodization so that its part 2o 3), and be formed naturally many pores in anodizing process in metal oxide layer, wherein filling metal (referring to Patent Document 4).
[correlation technique document]
[patent documentation]
[patent documentation 1]
No. 2006-514286, PCT Japan stage communique
[patent documentation 2]
No. 4347801, Jap.P.
[patent documentation 3]
No. 2006-145230, Japanese unexamined patent publication
[patent documentation 4]
No. 2005-172569, Japanese unexamined patent publication
[non-patent literature]
[non-patent literature 1]
Optics Express, the 17th volume, the 21st phase, the 18556th page
Summary of the invention
The manufacture method of micro concavo-convex metal construction is very complicated, and in the invention of the patent documentation 1～3 that adopts chemical etching formation micro concavo-convex structure, and, in the invention of the patent documentation 4 that adopts anodic oxidation formation micro concavo-convex structure, be difficult to formation and there is large-area micro concavo-convex metal construction.Therefore, think that the cost of substrate of unit area is very high.In addition, as very difficult in formed above-mentioned micro concavo-convex metal construction on the complicated substrates such as liquid container that formed by a plurality of protuberances and recess.
In view of above situation has been developed the present invention.An object of the present invention is to provide a kind of relatively large-area method thering is low cost fabrication optical electric field enhance device on the substrate of arbitrary shape of covering.
The method of manufacture optical electric field enhance device of the present invention comprises:
Film forms step, and this step forms the film formed by the first metal or metal oxide on substrate;
The micro concavo-convex structural sheet forms step, and this step is carried out hydro-thermal reaction and formed the micro concavo-convex structural sheet that the oxyhydroxide by the first metal or metal oxide forms by making to be formed at film on substrate; With
Metal level forms step, and this step forms the metal superfine concaveconvex structure layer consisted of the second metal on micro concavo-convex structural sheet surface.
Preferably, at metal level, form in step, form metal level as described metal superfine concaveconvex structure layer, there is the concaveconvex structure that shape is different from described micro concavo-convex structural sheet on the surface of described metal level.。
The second metal is preferably one of gold, silver, copper, aluminium and platinum or has the alloy of one of these metals as key component.Au and Ag are particularly preferred.
It can be the vapor deposited metal step that metal level forms step, and this step forms the metal level consisted of the second metal on micro concavo-convex structural sheet surface by vapour deposition.
In the second metal is golden situation, the thickness of the film that it is desirable to form by vapour deposition is more than 30nm.
In the second metal is silver-colored situation, the thickness of the film that it is desirable to form by vapour deposition is below 150nm.
The method of manufacture optical electric field enhance device of the present invention can also comprise after described metal level forms step:
Lamination step, this step will be different from one of bimetallic the 3rd metal and dielectric and be laminated on the metal superfine concaveconvex structure layer formed by the second metal.
In the method for manufacture optical electric field enhance device of the present invention, it can be the fine metal particle dispersion steps that metal level forms step, and the fine metal particle that this step will be formed by the second metal is dispersed on micro concavo-convex structural sheet surface.
Preferably the diameter of fine metal particle is below 100nm.
The first metal can be aluminium, and metal oxide can be aluminium oxide.
It is desirable to, oxyhydroxide is at least one in bayerite and boehmite.
The method of manufacture optical electric field enhance device of the present invention can obtain by following simple step the optical electric field enhance device of the metal construction with the micro concavo-convex section that is of a size of the tens nanometer magnitude: film forms step, and this step forms the film formed by the first metal or metal oxide on substrate; The micro concavo-convex structural sheet forms step, and this step is carried out hydro-thermal reaction and formed the micro concavo-convex structural sheet that the oxyhydroxide by the first metal or metal oxide forms by making to be formed at film on substrate; Form step with metal level, this step forms the metal superfine concaveconvex structure layer consisted of the second metal on micro concavo-convex structural sheet surface.
Because the optical electric field enhance device can obtain by these extremely simple steps, therefore with conventional device, to compare, manufacturing cost can be significantly reduced.
In addition, the substrate that each step can be applicable to have larger area and has arbitrary shape.Therefore, can manufacture the optical electric field enhance device that there is large-area optical electric field enhance device and there is desired shape.
When irradiation is on the lip-deep metal superfine jog of the optical electric field enhance device obtained by manufacture method of the present invention, described device can be induced local plasmon body excimer (localized plasmon) effectively in the metal superfine relief structured surface.Local plasmon body excimer produces the optical electric field enhancement effect.In addition, when irradiation is being positioned on the zone that the tested object on the optical electric field enhance device places, the light produced by this tested object will amplify by the optical electric field enhancement effect, make the light produced with high-sensitivity detection become possibility.The optical electric field enhance device can be advantageously used for the surface-enhanced Raman substrate that can effectively amplify Raman signal, to realize the raising of detection sensitivity.
The accompanying drawing explanation
Fig. 1 show to manufacture the intersection of sectional view of step that optical electric field strengthens the method for substrate.
Fig. 2 A is the skeleton view that electric field strengthens substrate 1, and it is the first embodiment of optical electric field enhance device of the present invention that electric field strengthens substrate 1.
Fig. 2 B is the enlarged drawing of a part of IIB of optical electric field shown in Fig. 2 A side surface that strengthens substrate 1.
Fig. 3 is the SEM photo on the surface of boehmite layer.
Fig. 4 A is the SEM photo on the surface (30nm is thick) of golden layer of vapour deposition.
Fig. 4 B is the SEM photo on the surface (60nm is thick) of golden layer of vapour deposition.
Fig. 4 C is the SEM photo on the surface (90nm is thick) of golden layer of vapour deposition.
Fig. 4 D is the SEM photo on the surface (150nm is thick) of golden layer of vapour deposition.
Fig. 4 E is the SEM photo on the surface (250nm is thick) of golden layer of vapour deposition.
Fig. 4 F is the SEM photo on the surface (400nm is thick) of golden layer of vapour deposition.
Fig. 5 A is the SEM photo on the surface (30nm is thick) of the silverskin of vapour deposition.
Fig. 4 B is the SEM photo on the surface (60nm is thick) of the silverskin of vapour deposition.
Fig. 5 C is the SEM photo on the surface (90nm is thick) of the silverskin of vapour deposition.
Fig. 5 D is the SEM photo on the surface (150nm is thick) of the silverskin of vapour deposition.
Fig. 5 E is the SEM photo on the surface (250nm is thick) of the silverskin of vapour deposition.
Fig. 5 F is the SEM photo on the surface (400nm is thick) of the silverskin of vapour deposition.
Fig. 6 is the figure that shows that Raman spectrum that the sample of the golden film (60nm is thick) with vapour deposition obtains distributes.
Fig. 7 is the figure that shows that Raman spectrum that the sample of the silverskin (60nm is thick) with vapour deposition obtains distributes.
Fig. 8 is the dependent figure of thickness of the Raman signal intensity that shows that sample with vapor deposition of gold film obtains.
Fig. 9 is the dependent figure of thickness of the Raman signal intensity that shows that sample with vapour deposition silverskin obtains.
Embodiment
Below, the embodiment of the method for manufacture optical electric field enhance device of the present invention is described with reference to the accompanying drawings.
Fig. 1 shows is that the optical electric field of manufacturing as the embodiment of optical electric field enhance device strengthens the method for substrate, and is the intersection of sectional view that shows each step of the method.
Prepare tabular transparency carrier main body 11.Use acetone and clean methanol transparency carrier main body 11.Afterwards, aluminium, as the first metal, is formed to the aluminium film 20 of approximately tens of nanometer thickness on transparency carrier main body 11 surfaces by sputtering method, this forms step for film.
Next, the transparency carrier main body 11 that has aluminium film 20 on it is immersed in the pure water of boiling, then take out after several minutes (approximately 5 minutes), this forms step for the micro concavo-convex structural sheet.Boiling is processed (hydro-thermal reaction) and is given the aluminium film 20 transparencys, and produces the transparent micro concavo-convex structural sheet 22 formed by bayerite or boehmite.
Next, by the second vapor deposited metal, on micro concavo-convex structural sheet 22, this forms step for metal level.
Adopt tabular substrate in above-mentioned example.Yet the step of the method can be applicable to the substrate of any required form.
Aluminium is to form at the micro concavo-convex structural sheet example that carries out the first metal of hydro-thermal reaction in step.As other selection, can adopt metal oxide, as aluminium oxide (Al (OH) 3).By aluminium or the aluminium oxide that carries out hydro-thermal reaction, can form by bayerite (Al[OH] 3) and/or the micro concavo-convex structure (with reference to Fig. 3) with complicated triangular pyramid structure that forms of boehmite (AlOOH).
As the substitute of aluminium, can adopt the metal (as titanium (Ti)) that forms the micro concavo-convex structure by carrying out hydro-thermal reaction, as the first metal.
In addition, the method film of the first metal or metal oxide is formed on substrate 11 is not limited to sputtering method.Alternatively, film can form by heating vapour deposition process or passing through sol-gal process.
Hydro-thermal reaction is not limited to boiling and processes.Process as an alternative, can will form the exposure of substrates of film of the first metal on it in high-temperature steam, so that the first metal reacts with high-temperature steam.
The second metal that forms metal superfine concaveconvex structure layer 24 can be to produce any metal of local plasmon body excimer when irradiating with exciting light.The example of this metal comprises: gold (Au), silver (Ag), copper (Cu), aluminium (Al), platinum (Pt) and have the alloy of these metals as its key component.Au and Ag are particularly preferred.
Fig. 2 A is the skeleton view that the display light electric field strengthens substrate 1.Fig. 2 B is the enlarged drawing of the part IIB of optical electric field shown in Fig. 2 A side surface that strengthens substrate 1.
As shown in Figure 2 A and 2 B, optical electric field strengthen substrate 1 by substrate 11, be arranged on the micro concavo-convex structural sheet 22 that there is in its surface micro concavo-convex structure 23 on substrate 11 and be formed at the lip-deep metal superfine concaveconvex structure of micro concavo-convex structure 23 layer (metal level) 24 and form.The resonance of local plasmon body excimer is induced by the light on the micro concavo-convex structure 25 that is radiated at metal superfine concaveconvex structure layer 24 (hereinafter being called exciting light), and produces by the resonance of local plasmon body excimer the optical electric field strengthened on metal superfine concaveconvex structure layer 24 surface.
It is zigzag cross section substantially that the transparent micro concavo-convex structure 23 formed by the oxyhydroxide as the metal hydroxides such as boehmite or metal oxide has, but the size of protuberance (size of peak angle) is different with direction.Can form metal superfine concaveconvex structure layer 24 on transparent micro concavo-convex structure 23, and there is average headway and the mean depth that is less than excitation wavelength.Note, the spacing of transparent micro concavo-convex structure 23 is the peak-to-peak distances that have the adjacent projection of recess between the two herein, and the degree of depth is the distance to the bottom of the recess be adjacent by the peak of protuberance.
Note, adopting as transparency carriers such as glass substrates as substrate 11 and in forming the situation of the transparent micro concavo-convex structural sheet 22 formed by bayerite or boehmite, can make exciting light be entered by front surface or the rear surface of substrate, with the surface at metal level 24, produce the photoelectricity enhanced field.In addition, also can be detected as flashlights such as Raman signal light by front surface or the rear surface of substrate.Herein, the transparent light referred to about irradiating light and producing about irradiating the caused tested object of light of term, transmissivity is more than 50%.Note, more preferably, about the light of these types, transmissivity is more than 75%, and then more preferably more than 90%.
Metal superfine concaveconvex structure layer 24 surface along micro concavo-convex structural sheet 22 form, and can have and the essentially identical micro concavo-convex structure of micro concavo-convex structure 23.Alternatively, the micro concavo-convex structure 25 of metal superfine concaveconvex structure layer 24 can have the jog that shape is different from the micro concavo-convex structure 23 of micro concavo-convex structural sheet 22, as shown in Fig. 2 B.
If the very thin thickness of the metal of vapour deposition in above-mentioned manufacture method, the micro concavo-convex structure of metal level will have and the essentially identical micro concavo-convex structure of the micro concavo-convex structure 23 of micro concavo-convex structural sheet 22.If the thickness of the metal of vapour deposition is very thick, metal superfine concaveconvex structure layer 24 will have following micro concavo-convex structure, and wherein the distance between adjacent projection is less than the distance between the corresponding protuberance of micro concavo-convex structure 23, as shown in Fig. 2 B.The protuberance 24a of metal superfine concaveconvex structure layer 24 is by sphering, and compares with the situation that wherein along the micro concavo-convex structure 23 of micro concavo-convex structural sheet 22, forms metal films, and the distance between adjacent projection is less.
Preferably there is following part, at described part place, in the micro concavo-convex structure 25 of metal superfine concaveconvex structure layer 24, between protuberance 25a and adjacent projection 25b, be distance W m, distance between the protuberance 23a of the micro concavo-convex structure 23 of substrate and protuberance 23b (corresponding with protuberance 25a and 25b) is Wb, and Wm is less than Wb, as shown in Fig. 2 B.Herein, distance W m between adjacent projection 25a and 25b is defined as the distance by peak to the following position of protuberance 25a of lower protuberance 25b, and described position has half depth D m/2 of depth D m of the deepest part of the recess 25c between adjacent projection 25a and 25b.Similarly, distance W b between adjacent projection 23a and 23b is defined as the distance by peak to the following position of protuberance 23a of lower protuberance 23b, and described position has half depth D b/2 of depth D b of the deepest part of the recess 23c between adjacent projection 23a and 23b.
The micro concavo-convex structure 25 of metal superfine concaveconvex structure layer 24 is following micro concavo-convex structures, wherein at least one in the length of the direction upper convex portion perpendicular to substrate and in being parallel to the length of direction upper convex portion of substrate is shorter than and excites light wavelength, makes on the surface of metal superfine concaveconvex structure layer 24 and can produce local plasmon body excimer.
Expectation, the protuberance of the structured metal layer 24 of protuberance and recess is the particulate that the gathering by metal forms.Expectation, the aspect ratio of fine-grannular protuberance (length on the direction of the length on the direction perpendicular to substrate/be parallel to substrate) is more than 0.5.
Note, what expect is, mean depth by peak to the bottom of the recess be adjacent of protuberance is below 200nm, and, in the micro concavo-convex structure 25 of metal superfine concaveconvex structure layer 24, the peak-to-peak average headway that has the adjacent projection of recess between the two is below 200nm.
On the micro concavo-convex structure at substrate by vapour deposition, form in the situation of metal superfine concaveconvex structure layer, preferably when using gold as metal thickness for 400nm below, and when using silver as metal thickness for 90nm below.Gold or silver-colored amount by vapour deposition corresponding to these thickness, can obtain the micro concavo-convex metal construction of the optical electric field that can produce effective enhancing.
Note, not must the micro concavo-convex structure of metal superfine concaveconvex structure layer in distance between all adjacent projection be less than the distance between adjacent projection in the micro concavo-convex structure of corresponding substrate.But, along with the increase of distance quantity of the adjacent projection of little metal superfine concaveconvex structure layer than the distance of adjacent projection in the micro concavo-convex structure of corresponding substrate, it is more remarkable that the optical electric field enhancement effect will become.
Particularly, if there is the distance between the adjacent projection of metal superfine concaveconvex structure layer 25, be the following zone of 20nm, will produce the extremely strong optical electric field enhanced field that be known as focus in this zone.For this reason, preferably having the distance between a large amount of adjacent projection is the following local of 20nm.
In above embodiment, employing be second metal of one deck only.Alternatively, can the two or more metals of lamination.In addition, dielectric layer can be pressed on the second metal.By the two or more metals of lamination or by the second metal overlayer piezoelectric dielectric, can give interference effect and anti-oxidation effect.That is, if certain phase matching of the thickness of structural sheet and light, light will be trapped in structural sheet by the interference of light effect, and can produce stronger optical electric field enhancement effect.In addition, by providing silver layer as the second metal and passing through metal-laminated on silver layer, the oxidation of silver can be inhibited.
Note, in the situation on dielectric layer being pressed in to the metal superfine concaveconvex structure layer formed by the second metal, expectation be that dielectric thickness is below 50nm.For example, can be by SiO 2thick layer with 10nm is pressed on metal superfine concaveconvex structure layer.
Above embodiment is described to adopt the situation of vapour deposition process as the method that forms metal superfine concaveconvex structure layer.Alternatively, can, by disperseing and arranging bimetallic subparticle, form metal superfine concaveconvex structure layer on micro concavo-convex structural sheet surface.
Preferably, from obtaining high optical electric field enhancement effect aspect, consider, the diameter of bimetallic subparticle is below 100nm.
Below fine metal particle to be disperseed and is fixed on the example of the method on the micro concavo-convex structural sheet.
1) fine metal particle is dispersed in organic solvent, colloidal solution is cast on the boehmite substrate, then dry;
2) polycation or cationic molecule film are adsorbed on the boehmite substrate, and fine metal particle are disperseed and be fixed on film by electrostatic interaction;
3) use thiol derivative to make the modification of boehmite substrate, and utilize the key of spontaneous formation between metal and sulphur that fine metal particle is fixed on the boehmite substrate; With
4) utilize the electronegative fact of fine metal particle, by electrophoresis, on the boehmite substrate, make fine metal particle assemble.
By the methods such as method as previously discussed, can obtain the micro concavo-convex metal construction, wherein fine metal particle disperses and is fixed on the micro concavo-convex structural sheet.
[embodiment]
Below will describe the result that optical electric field strengthens the concrete manufacture example of substrate 1 and adopts the raman spectroscopy measurement of measuring sample, it is an embodiment of optical electric field enhance device of the present invention that optical electric field strengthens substrate 1.
[manufacturing the method that optical electric field strengthens substrate]
Adopt glass substrate (BK-7:Eagle2000, from Corning) as transparency carrier main body 11.
For glass substrate main body 11, use acetone and use methyl alcohol to carry out respectively ultrasonic clean (45kHz) 5 minutes.Then, utilize sputtering equipment (from Canon Anelva) to form the thick aluminium 20 of 25nm on glass substrate 11.Note, adopt surface profile measuring instrument (from TENCOR) to measure the thickness of aluminium lamination, confirm that this thickness is 25nm (± 10%).
Afterwards, prepare pure water in water-bath (from Nishi Seiki K.K.) and make its boiling.Will on it, have the glass substrate main body 11 of aluminium lamination 20 immerse in boiling water, after 5 minutes by its taking-up.Now, in immersing boiling water, the glass substrate 11 by having aluminium lamination 20 on it after 1 minute～2 minutes, confirms aluminium bleach.This be because, by boiling, process, aluminium lamination becomes the micro concavo-convex structural sheet 22 formed by boehmite or bayerite.
What Fig. 3 showed is to use SEM (from the S4100 of Hitachi) to observe the result on the surface of boehmite layer 22.The white portion of Fig. 3 is protuberance, and grey color part is recess.The pattern of protuberance and recess is irregular, but has crossed over the whole surface of boehmite layer, and the internal homogeneity of micro concavo-convex structure is very high.Photo by the surface of the boehmite layer shown in Fig. 3 is appreciated that concaveconvex structure consists of a large amount of peaks shape protuberance.Note, the cross section of the concaveconvex structure of boehmite layer is zigzag, schematically shows as shown in Figure 2 B.
Finally, Au vapour deposition 30nm is thick by EB (electron beam) vapour deposition, on the surface of boehmite layer 22, has the sample of the structured metal layer of fine protuberance and recess 24 with generation.Note, also be manufactured on the sample of the Au that micro concavo-convex transparent configuration layer 22 surface upper deposition 60nm, 90nm, 150nm, 250nm and 400nm are thick, and deposit the sample of the Ag that 60nm, 90nm, 150nm, 250nm and 400nm are thick on micro concavo-convex transparent configuration layer 22 surface.Herein, measure in the following manner the thickness of vapour deposition: with sample, prepare dividually the detect thickness glass substrate, cover the part surface of each detect thickness with glass substrate, by being placed in to vapor deposition chamber with the substrate of glass substrate and sample, detect thickness carries out vapour deposition, detect thickness from vapour deposition is got next band with glass substrate, then measure by it not vapor deposited metal, band is stripped from the thickness of the surface at place to the metallic surface of vapour deposition.
On it vapour deposition the SEM photo on surface of each sample of Au be presented in 4A～4F, and on it vapour deposition the SEM photo on surface of each sample of Ag be presented in Fig. 5 A～5F.
In the situation of Au vapour deposition, increase along with the thickness of the gold formed by vapour deposition, protuberance is assembled also fine-grannular gradually, thereby forms the fine-grannular metal superfine concaveconvex structure that shape is different from micro concavo-convex structure 25 on bayerite or boehmite surface, as shown in Fig. 4 A～4F.When irradiation in shape the time, produces the extremely strong optical electric field that is called " focus " at these metallic fine particles between particulate, this strengthens in substrate in optical electric field is preferred.Along with the thickening of thickness, it is large that particulate becomes.As found out in Fig. 4 F, even when thickness is 400nm, the particulate shape also is maintained.
In the situation of Ag vapour deposition, along with the increase of the thickness of the silver formed by vapour deposition, the silver that thickness is 30nm～90nm forms the island structure as shown in Fig. 5 A～5C gradually, and is considered to silver film and flattens gradually.As shown in Fig. 5 D～5F, silver forms the larger fine-grannular structure of thickness in 150nm～400nm.
(the Raman look is penetrated the measurement of light)
The ethanolic solution that 100 μ l wherein is dissolved with to rhodamine 6G drops on the sample of each optical electric field enhancing substrate of manufacturing by said method.Make the solution drying, and utilize dry sample measurement Raman diffused light.
Raman diffused light utilizes micro-Raman spectroscopy (HR800) to detect.Adopt laser beam that peak wavelength is 785nm as excitation beam, and observed with the magnification of 20 times.Following object lens laser power afterwards closely is 0.5mW, and irradiation time is 10 seconds.
Fig. 6 and Fig. 7 are the figure that shows the Raman shifts spectral distribution detected by micro-Raman spectroscopy.Fig. 6 shows be it on vapour deposition the Raman spectrum that obtains of the sample of 60 μ m Au, and Fig. 7 demonstration be on it vapour deposition the Raman spectrum that obtains of the sample of 60 μ m Ag.
The sample (having shown what its Raman spectrum distributed in Fig. 6 and 7) that strengthens the method manufacture of substrate by manufacture optical electric field of the present invention can obtain extremely strong Raman signal.Note, with adopting gold, as bimetallic situation, compare, when adopting silver as the second metal, the sample with thinner vapour deposition thickness (30nm and 60nm) has obtained stronger Raman signal.
Fig. 8 is the 1360cm after white noise that removes drawn with respect to the Au vapour deposition film thickness as transverse axis -1the figure of peak strength, the Raman shifts spectral distribution that the drafting of this figure has utilized vapour deposition thereon each sample of Au to obtain by the Raman diffused light that detects the substrate front surface.
As shown in Figure 8, in golden film thickness is 30nm～90nm scope, along with the change of Au vapour deposition film thickness is large, obtain larger signal intensity.Along with the change of the vapour deposition film thickness of Au is large, Au forms the particulate shape, and the distance between protuberance diminishes, thereby forms a large amount of focuses that demonstration is known by institute in the SEM photo of Fig. 4 A～Fig. 4 C.These are considered to the reason that signal intensity increases.Simultaneously, as shown in Figure 8, when golden film thickness is 150nm～400nm, the signal intensity that signal intensity obtains when being 30nm～90nm at golden film thickness.The reason that signal intensity reduces it is believed that and be, optical electric field strengthens degree because particle size increases, particulate contacts with each other and be electrically connected each other continuous and deteriorated.Maximum when signal intensity is 90nm at thickness.But, obtain sufficient optical electric field enhancement effect when thickness is 150nm～400nm, and the Raman signal of amplification detected.
Fig. 9 is the 1360cm after white noise that removes drawn with respect to the Ag vapour deposition film thickness as transverse axis -1the figure of peak strength, the Raman shifts spectral distribution that the drafting of this figure has utilized vapour deposition thereon each sample of Ag to obtain by the Raman diffused light that detects the substrate front surface.
Be appreciated that when thickness become 150nm when above signal intensity sharply reduce, and in silver-colored situation picked up signal not substantially.It is former because think and be that signal intensity reduces, and similar to golden situation, optical electric field strengthens degree because particle size increases, particulate contacts with each other and be electrically connected each other continuous and deteriorated.In addition, when thickness is thinner, silver layer flattens gradually, and then silver further is accumulated on the silver layer flattened.Therefore, think that silver layer easily becomes to be electrically connected continuously, optical electric field intensity significantly reduces as a result.

Claims (11)

1. a method of manufacturing the optical electric field enhance device, described method comprises:
Film forms step, and described step forms the film formed by the first metal or metal oxide on substrate;
The micro concavo-convex structural sheet forms step, and described step is carried out hydro-thermal reaction and formed the micro concavo-convex structural sheet that the oxyhydroxide by described the first metal or described metal oxide forms by making to be formed at described film on described substrate; With
Metal level forms step, and described step forms the metal superfine concaveconvex structure layer consisted of the second metal on described micro concavo-convex structural sheet surface.
2. the method for manufacture optical electric field enhance device as claimed in claim 1, wherein:
Form in step at described metal level, form metal level as described metal superfine concaveconvex structure layer, there is the concaveconvex structure that shape is different from described micro concavo-convex structure on the surface of described metal level.
3. as the method for the described manufacture optical electric field of any one in claim 1 and 2 enhance device, wherein:
Described the second metal is one of gold, silver, copper, aluminium and platinum.
4. the method for manufacture optical electric field enhance device as described as any one in claim 1～3, wherein:
It is the vapor deposited metal step that described metal level forms step, and described vapor deposited metal step forms the metal level consisted of described the second metal on the surface of described micro concavo-convex structural sheet by vapour deposition.
5. the method for manufacture optical electric field enhance device as claimed in claim 4, wherein:
Described the second metal is gold; And
The thickness of the described film formed by vapour deposition is more than 30nm.
6. the method for manufacture optical electric field enhance device as claimed in claim 4, wherein:
Described the second metal is silver; And
The thickness of the described film formed by vapour deposition is below 150nm.
7. the method for manufacture optical electric field enhance device as described as any one in claim 1～6, after described metal level forms step, described method also comprises:
Lamination step, described step will be different from one of described bimetallic the 3rd metal and dielectric and be laminated on the described metal superfine concaveconvex structure layer formed by described the second metal.
8. the method for manufacture optical electric field enhance device as described as any one in claim 1～3, wherein:
It is the fine metal particle dispersion steps that described metal level forms step, and the fine metal particle that described fine metal particle dispersion steps forms described the second metal is dispersed on the surface of described micro concavo-convex structural sheet.
9. the method for manufacture optical electric field enhance device as claimed in claim 8, wherein:
The diameter of described fine metal particle is below 100nm.
10. the method for manufacture optical electric field enhance device as described as any one in claim 1～9, wherein:
Described the first metal is aluminium, and described metal oxide is aluminium oxide.
11. the method for manufacture optical electric field enhance device as described as any one in claim 1～10, wherein:
Described oxyhydroxide is at least one in bayerite and boehmite.
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105158228A (en) * 2015-07-30 2015-12-16 西北大学 SERS (Surface enhanced Raman Scattering) substrate based on boehmite nanometer film and preparation method thereof
CN108275651A (en) * 2018-01-22 2018-07-13 临沂大学 A kind of preparation method of surface enhanced Raman scattering substrate

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6145861B2 (en) 2012-08-15 2017-06-14 富士フイルム株式会社 Photoelectric field enhancement device, light measurement apparatus and method
JP2014190834A (en) * 2013-03-27 2014-10-06 Fujifilm Corp Optical field enhancement device and method for manufacturing the same
JP6229387B2 (en) * 2013-09-12 2017-11-15 大日本印刷株式会社 Optical member and manufacturing method thereof
JP6337127B2 (en) * 2014-08-27 2018-06-06 富士フイルム株式会社 Photoelectric field enhancement device and method for producing photoelectric field enhancement device
CN109073642A (en) 2015-09-17 2018-12-21 格哈德·马勒 Sensor device for biological sensing and other application
CN106093007A (en) * 2016-06-20 2016-11-09 上海理工大学 A kind of surface enhanced Raman scattering substrate and preparation method thereof

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4252843A (en) * 1977-02-18 1981-02-24 Minnesota Mining And Manufacturing Company Process for forming a microstructured transmission and reflectance modifying coating
JP2007240361A (en) * 2006-03-09 2007-09-20 Sekisui Chem Co Ltd Localized plasmon enhancing sensor
JP2009109395A (en) * 2007-10-31 2009-05-21 Fujifilm Corp Method of manufacturing fine structure, fine structure, device for raman spectrum, raman spectrometer, analyzing device, detection device and mass spectrometer
JP2009236830A (en) * 2008-03-28 2009-10-15 Sumitomo Precision Prod Co Ltd Analyte carrier and its manufacturing method
CN101646960A (en) * 2007-02-20 2010-02-10 佳能株式会社 Optical member, optical system using the same, and method for producing optical member

Family Cites Families (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4190321A (en) * 1977-02-18 1980-02-26 Minnesota Mining And Manufacturing Company Microstructured transmission and reflectance modifying coating
JPH09202649A (en) * 1996-01-24 1997-08-05 Central Glass Co Ltd Flower pedal-like transparent alumina membrane and its formation
US6406777B1 (en) * 2000-06-14 2002-06-18 The United States Of America As Represented By The Secretary Of The Navy Metal and glass structure for use in surface enhanced Raman spectroscopy and method for fabricating same
US6970239B2 (en) 2002-06-12 2005-11-29 Intel Corporation Metal coated nanocrystalline silicon as an active surface enhanced Raman spectroscopy (SERS) substrate
US7361313B2 (en) 2003-02-18 2008-04-22 Intel Corporation Methods for uniform metal impregnation into a nanoporous material
JP4163606B2 (en) 2003-12-10 2008-10-08 富士フイルム株式会社 Fine structure, method for producing fine structure, Raman spectroscopy method and apparatus
JP2006145230A (en) 2004-11-16 2006-06-08 Canon Inc Specimen carrier and its manufacturing method
CN102428359B (en) * 2009-03-04 2014-12-31 长谷川裕起 Assaying substrate with surface-enhanced raman scattering activity
US8427639B2 (en) * 2009-05-07 2013-04-23 Nant Holdings Ip, Llc Surfaced enhanced Raman spectroscopy substrates
US20110128535A1 (en) * 2009-11-30 2011-06-02 David Eugene Baker Nano-Structured Substrates, Articles, and Methods Thereof
JP5552007B2 (en) * 2010-09-17 2014-07-16 富士フイルム株式会社 Photoelectric field enhancement device
JP5553717B2 (en) * 2010-09-17 2014-07-16 富士フイルム株式会社 Light measuring method and measuring apparatus using photoelectric field enhancement device
JP2012132743A (en) * 2010-12-21 2012-07-12 Fujifilm Corp Optical electric-field reinforcing device and photodetector

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4252843A (en) * 1977-02-18 1981-02-24 Minnesota Mining And Manufacturing Company Process for forming a microstructured transmission and reflectance modifying coating
JP2007240361A (en) * 2006-03-09 2007-09-20 Sekisui Chem Co Ltd Localized plasmon enhancing sensor
CN101646960A (en) * 2007-02-20 2010-02-10 佳能株式会社 Optical member, optical system using the same, and method for producing optical member
JP2009109395A (en) * 2007-10-31 2009-05-21 Fujifilm Corp Method of manufacturing fine structure, fine structure, device for raman spectrum, raman spectrometer, analyzing device, detection device and mass spectrometer
JP2009236830A (en) * 2008-03-28 2009-10-15 Sumitomo Precision Prod Co Ltd Analyte carrier and its manufacturing method

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
JUNG-YEN YANG 等: "Surface-Enhanced Raman Scattering Active Substrates", 《IEEE NANOTECHNOLOGY MAGAZINE》 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105158228A (en) * 2015-07-30 2015-12-16 西北大学 SERS (Surface enhanced Raman Scattering) substrate based on boehmite nanometer film and preparation method thereof
CN105158228B (en) * 2015-07-30 2018-07-20 西北大学 SERS substrates and preparation method based on boehmite nano thin-film
CN108275651A (en) * 2018-01-22 2018-07-13 临沂大学 A kind of preparation method of surface enhanced Raman scattering substrate

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